Method for the determination of dialkyl phosphate metabolites in urine

Method for the determination of dialkyl phosphate metabolites in urine for studies of human exposure to malathion. Richard A. Fenske, and John T. Leff...
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J. Agric. Food Chem. 1989, 37,995-998

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Method for the Determination of Dialkyl Phosphate Metabolites in Urine for Studies of Human Exposure to Malathion Richard A. Fenske*J and John T. Leffingwel12

A method for reducing the mono- and dicarboxylic acid urinary metabolites of the organophosphorus pesticide malathion to dialkyl phosphates has been developed as a modification of a standard dialkyl phosphate metabolite procedure. Alkaline hydrolysis of urine samples is conducted prior to extraction and derivatization of dimethyl thiophosphate (DMTP) and dimethyl dithiophosphate (DMDTP). The dialkyl phosphates are derivatized with pentafluorobenzyl bromide (PFBB) and analyzed by GLC/ECD. Recoveries of malathion metabolites were 88%. The procedure was employed in the estimation of exposures in workers mixing and applying malathion in citrus orchards. This approach simplifies chromatographic analysis, increases sensitivity of the overall method, and allows investigators to assess human exposure to malathion within a general procedure for dialkyl phosphate metabolite analysis.

The use of urinary metabolites as a means of biological monitoring for pesticide exposure is gaining wide popularity in both scientific and regulatory circles (van Heemstra-Lequin and van Sittert, 1986; USEPA, 1987). However, animal dosing studies demonstrating substantial (>>50%)urinary excretion of the parent compound or major metabolites are an absolute prerequisite for validation of such a biological monitoring approach. The efficacy of urine excretion monitoring is improved if (1) the parent compound is excreted unchanged or as one or two major metabolites, (2) excretion is relatively rapid (